The interesting magnetic properties of cobalt polynuclear clusters arise from the paramagnetism of cobalt(II) ion, with the possibility to exhibit a strong Ising-type anisotropy. An efficient synthetic procedure of high-nuclearity clusters preparation is the use of carboxylate source and auxiliary ligands with bridging ability. Rezulting compounds are convenient objects for studying the type and magnitude of exchange interactions. Herein we report the structural characterization of a new octanuclear cobalt(II) pivalate cluster [Co8(OH)2(H2O)2(L)2(piv)12] (1), where L- is deprotonated 2,6-diformyl-p-cresol and piv – pivalate anion. The crystal structure consists of centrosymmetric octanuclear clusters co-crystallized with solvate MeCN molecules in 1:2 ratio. The coordination environment of the Co2+ atoms is different. Six of them (Co1, Co2, Co4 and symetrically related) are hexa-coordinated in slightly distorted octahedral geometry. Considering that chelating carboxylate groups occupy only one coordination position, the coordination geometry of Co3 and Co3‘ atoms can be described as distorted tetrahedral.